US2498875A - Coloring cellulosic materials with diazonium salts and naphthyl ethers - Google Patents

Description

UNITED STATES PATENT OFFICE COLORING CELLUIJOSIC MATERIALS WITH DIAZONIUM SALTS AND NAPHTHYL ETHERS Louis H. Bock, Huntingdon Valley, and Peter L.

de Bonneville, Philadelphia, Pa., assignors to Rolim & Haas Company," Philadelphia, Pa., a

corporation of Delaware No Drawing. Application August 19 1947,

. ,Serial No. 769,532 r 4 Claims.

fixation of color bodies ,orbolor-imparting groups on cellulosic fibers. or, other, cellulosicjmaterials. vMore particularly, this invention, deals with coupling a diazonium compound with. a naphthyl group having an ether group ,in the beta-position thereof and binding the naphthyl ether group to cellulose through a methylene linkage obtained from a quaternary ammonium methyl group carried by the naphthyl nucleus.

As a diazonium compound, there may beused one or more of the diazonium compounds obtained from. aromaticamines, such as aniline, chloroanilines, bromoanilines, nitroanilines, cyanoanilines, alkoxyanilines, C-alkylanilines, bromonitroanilines, bromoeC-alkylanilines, anthranilic esters, aminophthalic esters, aminobiphenyls, napthylamines, aminosulfonic acids," arylpolyamines, such as benzidine, phenylenediamine, dianisidine, diaminobiphenyls, and. thejlike. These amines yielddiazonium salts'ofthe formula AR(NiNX)n r where X is an anion sucli a's cl ilorine, bromine, nitrate, sulfate, 'etci," andn .is' a ,fsmallintege'r suchasone ortwo. I I g I The naphthyl ethers having a quaternary am: monium methyl group, as, a, ,substituent o'fthe cycleshavetheformula' wherein R is an alkyl group of one to eighteen carbon atoms; R, taken individually, is a methyl,

ethyl, benzyl, allyl, or methallyl group; R", taken H, '55 the 2 quaternary ammonium methyl form through halomethylation of ,a, naphthyl alkyl. ether fol; lowedby conversion of the halomethyl group to a quaternary ammonium methyl group. 'Ihis conversion may be accomplished by reactihn with a tertiary amine. Alternatively, the 'halomethy1, ated ether may be reacted with a, secondary amine to form a tertiary aminegroupwhi'ch'is then alkylated.

. In the first step the naphthylv alkylethers are halomethylated by reacting them with formaldehyde and a hydrogen halide in excess. Instead of formaldehye itself, there may be used a revertible polymer, such as alpha-trioxymethylene or other compound readily yielding formaldehyde, for example, a formal such asdimethylformalor diethyl formal. Chloromethyl ether orbromomethyl ether may also be used. The temperature of halomethylation may vary from 0" to'100 C. There maybe used an acidic catalyst, such as zinc chloride, sulfuric acid, or chlorosulfonic acid. An inert solvent such as a volatile hydrocarbon-or a chlorinated solvent may be used. l

Conversion of the halomethylated .naphthyl alkyl ether to a quaternary ammonium salt may be efiected by reaction withatertiary amine, directly or in the presence of'a. solvent. Typical tertiary amines are. trimethylamine, triethylamine, allyldimethylamine, methallyldimethylamine, allyldiethylamine, benzyldimethylamine,

benzyldiethylamine, pyridine, alpha-pipeline, quinoline, N-methylmorpholine, etc. 7

When the conversion is accomplished through reaction with a secondary amine followed by alkylation, there is used. an amine such as morpholine, pyrrolidine, piperidine, 'dimethylamine, diethylamine, benzyl methylamine, or other quite basic secondary amine. As alkylating agent, emay-be u d me h i d et y brqm a ethyl sulfate, allyl chloride, methallyl bromide, benzyl chloride, benzyl bromide, etc.

After a quaternary- ,salt has tbeen formed, it may be separated by evaporation of a, solvent, if used, and purified by crystallization, precipitation, treatment with charcoal, solvent extraction or other conventionalprocedure.

'-I {ypical preparations of .the. quaternary. am,- monium salts used in, this inventionlaraiveh in the following examples: 1 Y m; [J

a i Example 1 i Amixture was made from 5 0' partsby weight of betanaphthyl methyl ether, 20 partsof paraformaldehye, parts of concentrated "hydro- "chloric acid, and "1,60 parts'of carbon tetrac'lfioride. Hydrogen chloride gas was;,passed,ipr' an solid contained one chloromethyl grou-p'pernaph thyl group.

There were mixed 30 parts of this chloromethylnaphthyl methyl ether and19.6 parts of benzyldimethylamine together with 86v parts of benzene. The mixture was heated for eight hours at 50-60 C. It was then filtered. The solvent was evaporated to give 40 parts of a.colorless; water;-

V This reaction occurs when the quaternary amsoluble solid. Its equivalent weight by ionizable chlorine was 348 (theory for the benzyldimeth-- ylamine salt of chloromethyl naphthyl methyl ether is 342) Instead of the beta-naphthyl methyl ether there may be usedin the same way equivalent weights of beta-naphthyl butyl ether, beta-naphthyl octyl ether, beta-naphthyl dodecyl ether, beta-naphthyl. octadecyl ether, or other betanaphthyl'alkylether to yield the corresponding quaternary ammonium salts.

Example 2 maybe carried out with quino1ine,- or pyridine,

or other tertiary amine.

The naphthyl ethers may be represented by the formula where, the symbols havethe same, significance .as

7 before. ThecompoundmadeinExampleLhas the formula QCHSQ', oiofia' CHQCeHs CHi'-' CH N Cl CH3.-

while that of Example 2'has the structure Other quaternary, ammonium, methyl groups may beusedin-place of those used 'forgpurposes of illustration.

The naphthyl ether-reacts at its quaternary ammQniummethyLgrQupwith cellulose ZOI-I to form a celluloseether, thus.

monium compound is heated with a cellulosic compound having free hydroxyl groups. Temperatures of .120? C. to 170? C. are effective.

According to one procedure, cellulose is impregnated with a quaternary ammonium methyl naphthyl alkyl ether. For this purpose, preferably a 5% to 10% solution of such ether is applied to cellulosic fibers, yarns, or fabrics. Both weaker and stronger solutions may be so applied, however, depending upon the color intensity desired, solutions. from 1% to saturation being practical for application. Excess solution is removed therefrom, if desired, allowing a retention of 80% to of solution-based on the weight of the dry fabric. At this point the fabric may be dried and heated to efiect reactions between the ammonium methyl group and cellulose. The modified cellulose may then be treated with a diazonium compound in solution crsuspension. Color rapidly develops upon the modified cellulosic fiber, yarn, or fabric; The color body is attached through primary valence bonds directly to the modified cellulose. Excess or unreacted diazonium compound. is removed'by rinsing.

Alternatively, after the cellulosic material'has been treated with a solutionof a quaternary ammonium methyl naphthyl alkyl ether, it is treated with a diazonium compound to couple the diazonium compound and naphthyl ether on or in the presence of the cellulosic material. The thus-treated material;is then heated at 120 C. to1'70 C. to cause the reaction between cellulose and quaternary ammonium methyl group of the coupled ether. The same end result is had as by the first-described, method. In either case this inventionprovides-a new way of'fixing'azo dyes on cellulosic materials.

The concentration; of diazonium salts which are used may vary from-about"0;1'% to 2% or even more. It is generally desirable to supply molecular equivalents of such salts. for the naphthylcether on the cellulosic material. The solutions of diazonium salts aregenerally used at temperatures of 0 to 20C., as is common practice, although'in those cases where the diazonium salts are fairly stable, higher temperatures can frequently be advantageously utilized up to about 60." C.'.

The reactions here-described may be applied to cellulose in the form-of cotton, linen, ramie, sisal, hemp, regenerated cellulose in the form of rayon, cellulose .ethers having free alcoholic-type hydroxyl groups, etc., the cellulose materials being used remaining; intact up to at least C.

The invention.isi-illustrated by the following examples: v

- Example 3 meanwhile prepared: Asuspension was made of 18.3 parts by weight of 2,4-dinitroaniline in 142 parts ofynitric acid (sp; gr. 1.42) and the suspension cooled below 10 C. There was then added. 9.5, parts. of sodium metabisulfite. The

solution of diazonium salt" tl'ius obtained was for two hours. During this time a brownish color developed on the fabric.-The cloth was then washed with water and ,dried. The color was fast to washing. A

, In place of the dinitrober z enediazoniujrn zsalt used above there may be, used diazonium,.-salts from 2,5-dichloroaniline, o-nitroaniline, sulfanilic acid, benzidine, beta-naphthylamine, p-aminoacetophenone, or the like. Colors develop on the fabric carrying the methylnaphthyl ether group varying from yellow to brown, the particular color depending primarily upon the diazonium salt selected and applied.

Example 4 The benzyldimethyl quaternary ammonium chloride of methyl-beta-naphthyl methyl ether v was applied to a rayon fabric from a 5% solution. Excess solution was removed by centrifuging and the cloth was then passed into a chilled solution of dinitro-benzene diazonium nitrate, prepared as in Example 1 and diluted twentyfold with water. The naphthyl ether and diazonium compound coupled on the cellulose fabric. After the fabric had soaked for an hour in the solution of diazonium salt, it was removed, dried at 100 C. and heated for minutes at 150 C. The cloth was then washed. It was dyed brown. The dyeing was fast to washing with water and soap and to boiling in alcohol.

In place of the beta-naphthyl methyl ether used above there may be used other beta-naphthyl alkyl ethers. With large alkyl groups the same general results are obtained, the time of coupling being desirably increased. It has been found that times of one-half hour to six hours for coupling give good results. i

We claim:

1. A process for dyeing cellulosic material having free alcoholic hydroxyl groups which comprises the steps of treating a said material with a solution of a naphthyl ether, subsequently treating said material with a solution of a diazonium salt, and heating the cellulosic material carrying at least said naphthyl ether at 120 to 170 C., said naphthyl ether having the formula RI RI! I CHzN wherein R is an alkyl group of one to eighteen carbon atoms; R, taken individually, is a member of the class consisting of methyl, ethyl, allyl, methallyl, and benzyl groups; R", taken individually, is a member of the class consisting of methyl and ethyl groups; R, taken individually, is a member of the class consisting of methyl and ethyl groups; R" and R', taken together, represent a member of the class consisting of divalent saturated hydrocarbon chains of four to five carbon atoms and ether chains which jointly with the nitrogen form a heterocycle; R, R", and R', taken together, represent a trivalent unsaturated hydrocarbon group which jointly with the nitrogen atom forms a heterocycle; and X is an anion.

2. A process of dyeing cellulosic materials having free alcoholic hydroxyl groups which comprises treating said materials with a solution of "a naphthyl etherof the formula T" wherein R is an alkyl group of one to eighteen carbon atoms; R, taken individually, is a member of the, class consisting of methyl, ethyl, allyl, methallyl, and benzyl groups; R", taken individually, is a member of the class consisting of methyl and ethyl groups; R, taken individually, is a member of the class consisting of methyl and ethyl groups; R and R, taken together, represent a member of the class consisting of divalent saturated hydrocarbon chains of four to five carbon atoms and ether chains which jointly with the nitrogen atom form a heterocycle; R, R", and R, taken together, represent a trivalent unsaturated hydrocarbon group which jointly with the nitrogen atom forms a heterocycle; and X is an anion, treating said cellulosic materials carrying a said naphthyl ether with a solution of a diazoniu'm salt, and heating the treated cellulosic materials at to C. to react the cellulosic materials and naphthyl ether at the quaternary ammonium methyl group thereof.

3. A process of dyeing a cellulosic material having free alcoholic hydroxyl groups which comprises impregnating said material with a solution of a naphthyl ether of the formula wherein R is an alkyl group of one to eighteen carbon atoms; R, taken individually, is a member of the class consisting of methyl, ethyl, allyl, methallyl, and benzyl groups; R", taken individually, is a member of the class consisting of methyl and ethyl groups; vR, taken individually, is a member of the class consisting of methyl and ethyl groups; R" and R", taken together, represent a member of the class consisting of divalent saturated hydrocarbon chains of four to five carbon atoms and ether chains which jointly with the nitrogen atom form a heterocycle; R, R", and R, taken together, represent a trivalent unsaturated hydrocarbon group which jointly with the nitrogen atom forms a heterocycle; heating the resulting impregnated cellulosic material at 120 to 170 C. to react said material with said naphthyl ether, and treating said reacted material with a solution of a diazonium salt.

4. A process of dyeing a cellulosic material having free alcoholic hydroxyl groups which comprises impregnating said material with a solution of a naphthyl ether of the formula OOH:

iCtHI CH:N

7 8 .treatingrsaid .material with a solutionaof a-kad-ia- 1REFERJBNGES'GIT ED zomum salt, and heatmg sa1d;mater1a1..together following references areflofrecordvinrthe with said naphthyl ether at 120 to 170 C. until a reaction has taken place ,between said cellufile of mus patent losic material and said ether at its quaternary 5 UNITED: STATES PATENTS ammonium methyl. group. Number Name Date 1,886,480 Haller Nov. 8, 1932 LOUIS BOCK- '2,123,154 Schirm July 5, 1938 PETER DE BENNEVILLE- 12,13637'7 Dinklage Nov.15,1938

Claims (1)

1. A PROCESS FOR DYEING CELLULOSIC MATERIAL HAVING FREE ALCOHOLIC HYDROXY GROUPS WHICH COMPRISES THE STEPS OF TREATING A SAID MATERIAL WITH A SOLUTION OF A NAPHTHYL ETHER, SUBSEQUENTLY TREATING SAID MATERIAL WITH A SOLUTION OF A DIAZONIUM SALT, AND HEATING THE CELLULOSIC MATERIAL CARRYING AT LEAST SAID NAPHTHYL ETHER AT 120* TO 170*C., SAID NAPHTHYL ETHER HAVING THE FORMULA